CN102557889A - Method for synthesizing polyglycerol by using load type sodium hydroxide solid alkali catalyst - Google Patents
Method for synthesizing polyglycerol by using load type sodium hydroxide solid alkali catalyst Download PDFInfo
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- CN102557889A CN102557889A CN2012100045323A CN201210004532A CN102557889A CN 102557889 A CN102557889 A CN 102557889A CN 2012100045323 A CN2012100045323 A CN 2012100045323A CN 201210004532 A CN201210004532 A CN 201210004532A CN 102557889 A CN102557889 A CN 102557889A
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Abstract
The invention relates to a method for synthesizing polyglycerol by using a load type sodium hydroxide (NaOH) solid alkali catalyst. The method comprises the following steps: 1, preparing the load type NaOH solid alkali catalyst; and 2, synthesizing the polyglycerol, namely pouring the polyglycerol into a three-necked flask, adding the load type NaOH solid alkali catalyst in an amount which is 1 to 10 percent of the weight of the polyglycerol, reacting at the oil bath heating temperature of 220 and 260 DEG C for 3 to 6 hours, filtering, performing acid neutralization by using hydrochloric acid, distilling the obtained filtrate, and evaporating water to obtain the product. The method has the technical effects as follows: 1, a liquid NaOH catalyst is replaced by a solid alkali NaOH/gamma-Al2O3 or NaOH/ZrO2 catalyst, so that the product after the reaction is separated from the catalyst simply; and 2, the solid alkali catalyst is used, so that the alkalinity of the product in the reaction and after the reaction is greatly reduced, corrosion to the equipment is reduced, and environmental pollution is reduced. The process is reasonable and environment-friendly.
Description
Technical field
The present invention relates to a kind of preparation method of poly-glycerol, relate in particular to a kind of method that adopts the synthetic poly-glycerol of loading type sodium hydrate solid alkaline catalysts.
Background technology
Poly-glycerol is mainly derived from the glycerine industrial by-products; Then directly prepare by glycerine in a large number now, purposes is widely arranged, as can directly being used as thickening material, wetting Agent for Printing Inks; Its nitric ether is senior liquid explosive, and its acetic ester can be made the softening agent of PVC and cellulose materials.Poly-glycerol has been used for the manufacturing of makeup, washing composition, foodstuffs industry and macromolecular material etc.
Glycerine (1,2,3-trihydroxy-propyl alcohol) molecule has three hydroxyl groups groups, under the condition that catalyzer exists, can take place between the glycerol molecule mutual between dehydration condensation generation poly-glycerol.
At present, the preparation method of poly-glycerol is generally: under protection of inert gas such as nitrogen or carbonic acid gas, add a certain amount of catalyzer in the raw material, be warming up to 200～280 ℃ of reactions 2～10 hours, can prepare the product poly-glycerol of certain polymerization degree.Catalyst system therefor is generally liquid acid or alkaline matter is good with the liquid sodium hydroxide effect wherein.The advantage of this method is that method is ripe, raw material is sufficient, cheap; Reaction times is short; Low for equipment requirements, but also exist simultaneously a lot of shortcomings for example post catalyst reaction and product separation difficulty, liquid alkali catalyst to equipment corrosion severity, contaminate environment etc.
If can replace liquid alkali catalyst with solid base catalyst in the reaction process; The separation problem of post catalyst reaction and product is become simply, and avoided liquid acid base pair corrosion on Equipment problem, make that synthesizing of poly-glycerol is more simple; Environmental friendliness, more energy-conservation.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts the synthetic poly-glycerol of loading type sodium hydrate solid alkaline catalysts.
The objective of the invention is to realize like this, its method steps is:
1, the preparation of loading type NaOH solid base catalyst: aluminum oxide or Zirconia carrier are put into about baking oven baking 12h, removed the moisture and the impurity component of carrier inside, help the adsorption activity component.With the NaOH solid base catalyst of equi-volume impregnating preparation different dipping concentration (10% ~ 50%), after placement is flooded 24h at ambient temperature, under the irradiation of ir lamp, redundant moisture is evaporated, make the catalyzer substantially dry.To be close to the catalyzer that exsiccant respectively floods concentration then and put into more than the baking oven baking 16h, redundant moisture is all evaporated, form solid base catalyst.After from baking oven, taking out, put into about the retort furnace the inside pyroprocessing 3h of 700 ° of C environment, cooling prepares NaOH/Al
2O
3, NaOH/ZrO
2Solid catalyst.
2, poly-glycerol is synthetic: pour poly-glycerol into there-necked flask, adding is stirred than the load type solid body base catalyst of the NaOH of the weight 1% ~ 10% of poly-glycerol; In there-necked flask, feed protective gas nitrogen simultaneously, the oil bath Heating temperature is 220 ~ 260 ℃, and the reaction times is 3 ~ 6 hours; Behind the stopped reaction, filter hydrochloric acid acid neutralization; Gained filtrating is distilled, after wherein moisture steams, obtain product.The polymerization degree of product is 3 ~ 8.
3, the mensuration of the polymerization degree: the polymerization degree of the finished product poly-glycerol adopts the diacetyl oxide volumetry to confirm.
This technology has the following advantages:
1, with solid alkali NaOH/ γ-Al
2O
3Or NaOH/ZrO
2Catalyzer substitutes liquid NaOH catalyzer, makes to react after product and become simple separating of catalyzer.
2, owing to used solid base catalyst, reach the alkalescence that finishes after product during reaction is carried out and reduce significantly, thereby alleviated, reduced pollution environment to corrosion on Equipment.Technology is more reasonable, more environmental friendliness.
Embodiment
The present invention will be described further through following examples.
Instance one: (1) solid base catalyst NaOH/Al
2O
3Preparation: get Al
2O
3It is 10% NaOH solution that 15g adds concentration, mixes, and places to flood at ambient temperature behind the 24h under the irradiation of ir lamp, and redundant moisture is evaporated, and makes the catalyzer substantially dry.To be close to the exsiccant catalyzer then and put into more than the baking oven baking 16h, redundant moisture is all evaporated, form solid base catalyst.After from baking oven, taking out, put into about the retort furnace the inside pyroprocessing 3h of 700 ° of C environment, cooling prepares NaOH/Al
2O
3
(2) poly-glycerol is synthetic: take by weighing poly-glycerol 100.00g, NaOH/Al
2O
3Sample 16g adds in the three-necked flask, stirs nitrogen protection simultaneously, and the oil bath Heating temperature is 260 ℃, and the reaction times is 3 hours.
(3) filter: reaction finishes the back product is carried out suction filtration, and catalyzer is separated with poly-glycerol.Gained filtrating neutralizes with hydrochloric acid.
(4) distillation: the filtrating to after the neutralization is distilled, and contained humidity is removed in will filtrating, and obtains the pure article of poly-glycerol.Adopt the diacetyl oxide volumetry that its polymerization degree is demarcated, the polymerization degree is 4.24.
Instance two: (1) solid base catalyst NaOH/Al
2O
3Preparation: get Al
2O
3It is that 25% NaOH solution equal-volume mixes that 20g adds concentration, places to flood at ambient temperature behind the 24h under the irradiation of ir lamp, and redundant moisture is evaporated, and makes the catalyzer substantially dry.To be close to the exsiccant catalyzer then and put into more than the baking oven baking 16h, redundant moisture is all evaporated, form solid base catalyst.After from baking oven, taking out, put into about the retort furnace the inside pyroprocessing 3h of 700 ° of C environment, cooling prepares NaOH/Al
2O
3
(2) poly-glycerol is synthetic: take by weighing poly-glycerol 100.10g, NaOH/Al
2O
3Catalyzer 16g adds in the three-necked flask, stirs nitrogen protection simultaneously, and the oil bath Heating temperature is 260 ℃, and the reaction times is 3 hours.
(3) filter: reaction finishes the back product is carried out suction filtration, and catalyzer is separated with poly-glycerol.Gained filtrating neutralizes with hydrochloric acid.
(4) distillation: the filtrating to after the neutralization is distilled, and contained humidity is removed in will filtrating, and obtains the pure article of poly-glycerol.Adopt the diacetyl oxide volumetry that its polymerization degree is demarcated, the products obtained therefrom polymerization degree is 5.04.
Instance three: (1) solid base catalyst NaOH/ZrO
2Preparation: get carrier ZrO
2It is that 20% NaOH solution equal-volume mixes that 20g adds concentration, places to flood at ambient temperature behind the 24h under the irradiation of ir lamp, and redundant moisture is evaporated, and makes the catalyzer substantially dry.To be close to the exsiccant catalyzer then and put into more than the baking oven baking 16h, redundant moisture is all evaporated, form solid base catalyst.After from baking oven, taking out, put into about the retort furnace the inside pyroprocessing 3h of 700 ° of C environment, cooling prepares NaOH/ZrO
2Solid base catalyst
(2) poly-glycerol is synthetic: take by weighing poly-glycerol 100.00g, solid base catalyst NaOH/ZrO
216g adds in the three-necked flask, stirs and feeds nitrogen protection simultaneously, and the oil bath Heating temperature is 260 ℃, and the reaction times is 3 hours.
(3) filter: reaction finishes the back product is carried out suction filtration, and catalyzer is separated with poly-glycerol.Gained filtrating neutralizes with hydrochloric acid.
(4) distillation: the filtrating to after the neutralization is distilled, and contained humidity is removed in will filtrating, and obtains the pure article of poly-glycerol.Adopt the diacetyl oxide volumetry that its polymerization degree is demarcated, the products obtained therefrom polymerization degree is 5.9.
Claims (2)
1. method that adopts the synthetic poly-glycerol of loading type sodium hydrate solid alkaline catalysts is characterized in that method steps is:
1) preparation of loading type NaOH solid base catalyst: aluminum oxide or Zirconia carrier are put into about baking oven baking 12h, removed the moisture and the impurity component of carrier inside, use equi-volume impregnating preparation dipping concentration is 10% ~ 50% NaOH solid base catalyst; After placement is flooded 24h at ambient temperature, under the irradiation of ir lamp, redundant moisture is evaporated; Make NaOH solid base catalyst substantially dry; Then the NaOH solid base catalyst is put into more than the baking oven baking 16h, redundant moisture is all evaporated, after from baking oven, taking out; Put into about the retort furnace the inside pyroprocessing 3h of 700 ° of C environment, cooling prepares NaOH/Al
2O
3Or NaOH/ZrO
2Solid catalyst.
2. poly-glycerol is synthetic: pour poly-glycerol into there-necked flask, adding is stirred than the load type solid body base catalyst of the NaOH of the weight 1% ~ 10% of poly-glycerol; In there-necked flask, feed protective gas nitrogen simultaneously, the oil bath Heating temperature is 220 ~ 260 ℃, and the reaction times is 3 ~ 6 hours; Behind the stopped reaction, filter hydrochloric acid acid neutralization; Gained filtrating is distilled, after wherein moisture steams, obtain product, the polymerization degree of product is 3 ~ 8.
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| CN2012100045323A CN102557889A (en) | 2012-01-09 | 2012-01-09 | Method for synthesizing polyglycerol by using load type sodium hydroxide solid alkali catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657626A (en) * | 2012-09-03 | 2014-03-26 | 东华理工大学 | Preparation method of Al2O3/CaMgO composite solid base catalyst |
| CN107011198A (en) * | 2017-03-30 | 2017-08-04 | 南通沃兰化工有限公司 | One kind synthesis N, the technique of N dimethyl acetamides |
| CN109550491A (en) * | 2018-11-07 | 2019-04-02 | 山东科技大学 | Prepare ZrO2The method of catalyst |
| CN113509946A (en) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | Supported alumina solid base catalyst |
| CN115504865A (en) * | 2022-10-09 | 2022-12-23 | 广东工业大学 | Method for catalytically synthesizing oligoglycerol by solid base catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010105966A (en) * | 2008-10-30 | 2010-05-13 | Sakamoto Yakuhin Kogyo Co Ltd | Process for producing polyglycerin |
-
2012
- 2012-01-09 CN CN2012100045323A patent/CN102557889A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010105966A (en) * | 2008-10-30 | 2010-05-13 | Sakamoto Yakuhin Kogyo Co Ltd | Process for producing polyglycerin |
Non-Patent Citations (2)
| Title |
|---|
| ANDREAS MARTIN ET AL.: "Oligomerization of glycerol-a critical review", 《EUR.J.LIPID SCI.TECHNOL》, vol. 113, 31 December 2011 (2011-12-31), pages 100 - 117 * |
| ARNO BEHR ET AL.: "Improved utilisation of renewable resources：New important derivatives of glycerol", 《GREEN CHEMISTRY》, vol. 10, 31 December 2008 (2008-12-31), pages 13 - 30 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657626A (en) * | 2012-09-03 | 2014-03-26 | 东华理工大学 | Preparation method of Al2O3/CaMgO composite solid base catalyst |
| CN107011198A (en) * | 2017-03-30 | 2017-08-04 | 南通沃兰化工有限公司 | One kind synthesis N, the technique of N dimethyl acetamides |
| CN107011198B (en) * | 2017-03-30 | 2019-03-05 | 南通沃兰化工有限公司 | A kind of technique synthesizing n,N-dimethylacetamide |
| CN109550491A (en) * | 2018-11-07 | 2019-04-02 | 山东科技大学 | Prepare ZrO2The method of catalyst |
| CN113509946A (en) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | Supported alumina solid base catalyst |
| CN115504865A (en) * | 2022-10-09 | 2022-12-23 | 广东工业大学 | Method for catalytically synthesizing oligoglycerol by solid base catalyst |
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Application publication date: 20120711 |